Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof

ABSTRACT

A saturated polymer having a terminal aldehyde or hydroxy substituent which may be used directly or in a derivative form as a dispersant for both fuel and lubricating oil compositions, wherein the saturated polymer has a M n  of about 300 to 10,000, and is derived from a polyolefin which is derived from a monomer of the formula H 2  C=CHR 4 , wherein R 4  is hydrogen or a straight or branched chain alkyl radical, and wherein the polyolefin has at least about 30% terminal vinylidene unsaturation. Particularly desirable amine derivatives can be formed by either a single step aminomethylation process or a two step hydroformylation and reductive amination process.

This is a division, of application Ser. No. 08/662,835 filed on Jun. 12,1996 AND 08/206,993 filed on Mar. 7,1994,abandoned.

FIELD OF THE INVENTION

This invention relates to improved oil soluble dispersant additivesuseful in both fuel and lubricating oil compositions produced by thehydroformylation of certain olefin-terminated polymers to yieldpolymeric alcohols and aldehydes, and to further derivatizing thesefunctional polymers to obtain aminated polymers. This invention alsorelates to the direct production of aminated polyolefins by means of aone step aminomethylation process.

BACKGROUND OF THE INVENTION

Dispersants keep insolubles within the oil suspension, thus preventingsludge flocculation and precipitation. Suitable dispersants include, forexample, dispersants of the ash-producing and ashless type. Derivatizedolefinic polymers have been used as ashless dispersants andmultifunctional viscosity index improvers in lubricant and fuelcompositions.

In the lubricating oil sector, these are generally referred to asashless dispersants, and, in the case of the polybutylphenols, asMannich dispersants. The purpose of these dispersants is to keep insuspension oil-insoluble combustion residues, and thereby preventdeposits on metal surfaces, thickening of the oil and sludge deposits inthe engine and to avoid corrosive wear by neutralizing acidic combustionproducts.

In the motor fuel sector, the secondary products are generally referredto as carburetor or valve detergents. Their task is to free the entireintake system from deposits, to prevent further deposits and to protectthe system from corrosion.

Functionalized olefinic polymers are particularly useful as additives infuels and lubricating oils. Fuels include normally liquid petroleumfuels such as middle distillates boiling from 65° C. to 430° C.,including kerosene, diesel fuels, home heating oil, jet fuels, etc. Aconcentration of the additives in the fuel is in the range of typicallyfrom 0.0001 to 0.5and preferably from 0.005 to 0.15 wt. %, based on thetotal weight of the composition.

Additives may also be used in lubricating oil compositions which employa base oil in which the additives are dissolved or dispersed therein.Such base oils may be natural or synthetic. Base oils suitable for usein preparing the lubricating oil compositions include thoseconventionally employed as crankcase lubricating oils for spark-ignitedand compression-ignited internal combustion engines, such as automobileand truck engines, marine and railroad diesel engines, and the like.Advantageous results are also achieved by employing such additives inbase oils conventionally employed in and/or adapted for use as powertransmitting fluids, universal tractor fluids and hydraulic fluids,heavy duty hydraulic fluids, power steering fluids and the like. Gearlubricants, industrial oils, pump oils and other lubricating oilcompositions can also benefit from the incorporation therein of theadditives of the present invention.

Functional polymers having a number average molecular weight (M_(n)) inthe range of 700-5,000 have been used as intermediates in the synthesisof dispersants (i.e., additives) for fuel and lubrication applications.The most common functional groups are cyclic anhydrides, carboxylicacids, and phenols. These groups could be further elaborated to imides,and amides and Mannich based products with a variety of polyamines.

A conventional method of preparing polymeric acids and anhydridesgenerally involves pericyclic reactions of α,β-unsaturated carbonylcompounds with polymeric olefins either directly or in the presence ofchlorine. These reactions often lead to the incorporation of more thanone functional group per polymer.

The cobalt or rhodium-mediated hydroformylation of olefin polymers hasbeen utilized to a more limited extent to prepare alcohols andaldehydes. Use of the hydroformylation process results in theconsumption of the carbon-carbon double bond during the reaction,thereby introducing only one functional group per polymer in the absenceof diene comonomers.

US-A 3311598 (Mertzweiller et al.), which issued on Mar. 28, 1967,discloses the hydroformylation of a multi-olefinic hydrocarbon polymerwith carbon monoxide, and hydrogen, in the presence of catalystcontaining a transition metal selected from Group VIII of the PeriodicChart, to form hydroxylated (-CH₂ OH) and/or carbonyl (-CHO) derivativesof the polymer. The polymer is preferably either a polymer ofpolybutadiene, polycyclopentadiene, polyisoprene, and mixtures thereof,a butadiene-styrene copolymer, a pentadiene-styrene copolymer, or anisoprene-styrene copolymer.

Polyisobutene derivatives (e.g., polyisobutylamines) have frequentlybeen described in the literature and are used worldwide on a large scaleas lubricant and motor fuel additives. The intermediates for thepreparation of such additives are polybutenyl chloride,polybutenylsuccinic anhydride and polybutylphenols. See US-A 4859210(Franz et al.), which issued on Aug. 22, 1989, and US-A 4832702 (Kummeret al.), which issued on May 23, 1989, and WO-A 90/05711, published onMay 31, 1990.

The efficiency of the hydroformylation reaction as applied topolyisobutylene (PIB) varies with the type of polymer, and conversionsrange from 59-81% with the most reactive PIB's available (see US-A4832702). It would be highly desirable to increase the rate ofconversion in the hydroformylation of polyolefins to as close to 100% asis technically feasible.

The present inventors have discovered that olefinic polymers preparedwith a metallocene catalyst are especially suited for use in thehydroformylation process and synthesize of unique polymeric alcohols andaldehydes in substantially higher yields than even the reactive PIB's onan equal weight percent basis.

Unfortunately, hydroformylation has been observed to produce undesirableside products. Attempts to produce polymer aldehyde in high yield frommetallocene catalyzed olefinic polymers and vinylidene containing modelshas shown that 15-20% of the olefin is typically hydrogenated usingcobalt catalyst; furthermore, there a conversion-dependent loss ofaldehyde to alcohol which also limits the yield of aldehyde availablefor reductive amination. The present inventors have also discovered thatamine derivatives may be prepared in substantially higher yields bysubjecting the metallocene-catalyzed olefinic polymers toaminomethylation in a single step rather than the conventional two stepprocess of hydroformylation followed by reductive amination.

SUMMARY OF THE INVENTION

A saturated polymer having a terminal aldehyde or hydroxyl substituent,a M_(n) of about 300 to 10,000, and derived from a polyolefin derivedfrom a monomer of the formula H₂ C=CHR⁴ wherein R⁴ is hydrogen or astraight or branched chain alkyl radical. The polyolefin preferably hasat least about 30% terminal vinylidene unsaturation.

This polyolefin is formed from the reaction product of alkene andα-olefin monomers in the presence of a metallocene catalyst. Preferredpolyolefins are ethylene/α-olefin, a propylene/butene-1 copolymer, or abutene-l polyolefin.

Alternatively, the substituent of the saturated polymer is alkylamine.In this instance, the preferred polyolefin is a butene homopolymer, anethylene/propylene copolymer, or an ethylene/butene copolymer.

The present invention also includes a saturated polymer having aterminal alkylamino substituent, a Mn of about 300 to 10,000, andderived from a polyolefin derived from a monomer of the formula H₂C=CHR⁴ wherein R⁴ is hydrogen or a straight or branched chain alkylradical. Preferably, this polyolefin has at least about 30% terminalvinylidene unsaturation.

Furthermore, the present invention includes a polymeric hydroformylationalcohol or aldehyde reaction product which is formed by the reaction of:a polyolefin having Mn of about 300 to 10,000 and derived from a monomerof the formula H₂ C=CHR⁴, wherein R⁴ is hydrogen or a straight orbranched chain alkyl radical; hydrogen; and carbon monoxide in thepresence of a hydroformylation catalyst. Preferably, the polyolefin hasat least 30% terminal vinylidene unsaturation.

The hydroformylation reaction preferably occurs at a temperature in therange between about 25 to 200° C. and a pressure in the range betweenabout 1 to 350 bars. This hydroformylation reaction is, optionally,followed by reductive amination of the hydroformylation polymericreaction product, whereby a saturated polymer having an alkylaminosubstituent is formed.

Alternatively, an alkylamino substituted polymer dispersant can beformed in a single step aminomethylation process wherein an amine ismixed together with the polymer and syn gases in the presence of a noblemetal catalyst. The noble metal catalyst is preferably selected from thegroup consisting of: rhodium, ruthenium, rhenium and mixtures thereof.This aminomethylation reaction typically occurs at a temperature in therange between about 25 to 200° C. and a pressure in the range betweenabout 1 to 100 bars.

The polymeric hydroformylation reaction product can be furthercyanoalkylated and hydrogenated.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Unique polymeric aldehydes and alcohols can be synthesized by thehydroformylation of polyolefins formed from the reaction product ofalkene and α-olefin (up to C₁₆) monomers in the presence of ametallocene catalyst. Preferred polyolefins are ethylene/α-olefinhomopolymers and copolymers, a propylene/butene-1 copolymer, or abutene-1 polyolefin. These polymeric aldehydes and alcohols areparticularly useful as products or intermediates for lubrication andfuel dispersants.

The hydroformylation reaction of an ethylene-α- olefin polymer (EP),carbon monoxide, and hydrogen in the presence of dicobalt octacarbonylcatalyst (Co) is set forth below, wherein the hydroformylation step isfollowed by a reductive amination step to produce amine derivatives ofthe resultant polymeric aldehyde product. The hydroformylation andreductive amination process is hereafter referred to as "the two stepprocess". ##STR1##

It is also possible, and in many instances preferable, to conduct asingle (or "one step process") aminomethylation step wherein a higherconversion of the aldehyde to its derivatized amine product is observed.An aminomethylation reaction in the presence of a rhodium dicarbonylacetylacetonate catalyst is set forth below. ##STR2##

The overall aminomethylation process can be formally divided into threereactions. The first is hydroformylation leading to the formation of apolymeric aldehyde followed by condensation, resulting in theintermediate formation of Schiff's base or enamine, and subsequentlyhydrogenation of the C=N or C=C--N bond, respectively, producing thedesired end 10 product amine. The typical aminomethylation mechanism isbelieved to be as follows: ##STR3##

The present inventors have discovered that when the one stepaminomethylation process is used to produce polyamines from metallocenecatalyzed α-olefin polymers, it is less desirable to use a cobaltcatalyst as the hydroformylation catalyst. That is, the cobalt catalystis altered when an amine is added thereto. This is because the aminedeactivates the cobalt catalyst, thereby making it ineffective as ahydrogenation catalyst and thus inhibiting hydroformylation. It isnecessary when running the one step aminomethylation process to use acatalyst of rhodium, ruthenium, rhenium or mixtures thereof, which doesnot deactivate in the presence of amines. A preferred catalyst isrhodium with or without ligands, such as phosphines. Phosphinescontaining a carboxylic acid group can be used to change the solubilitycharacteristics of the rhodium by alternatively neutralizing andacidifying as a means of recovering the rhodium. The rhodium can beanchored to solid substances as well. One suitable method is through theuse of phosphines containing sulfonate groups which can be anchored onmacroporous glass substrates.

Cobalt catalysts can still be used in the two step process, so long asthere is a cobalt catalyst recovery step prior to the reductiveamination of the resulting polymeric aldehyde and alcohol. However, thetwo step process has the additional drawbacks of (1) paraffin formationmay be unacceptably high, and (2) conversion to the selected polymericamine will be reduced by the need to avoid alcohol formation.

METALLOCENE CATALYST

The catalyst for the production of polyolefins is preferably a bulkyligand transition metal compound. The bulky ligand may contain amultiplicity of bonded atoms, preferably carbon atoms, forming a groupwhich may be cyclic with one or more optional heteroatoms. The bulkyligand may be a cyclopentadienyl derivative which can be mono- orpolynuclear. One or more bulky ligands may be bonded to the transitionmetal atom. The transition metal atom may be a Group IV, V or VItransition metal comprehensively presented in "Advanced InorganicChemistry," F.A. Cotton, G. Wilkinson, Fifth Edition, 1988,John Wiley &Sons). Other ligands may be bonded to the transition metal, preferablydetachable by a cocatalyst such as a hydrocarbyl or halogen leavinggroup. The catalyst is derivable from a compound of the formula:

     L!.sub.m M S!.sub.n

wherein L is the bulky ligand, X is the leaving group, M is thetransition metal and m and n are such that the total ligand valencycorresponds to the transition metal valency. Preferably the catalyst isfour coordinate such that the compound is ionizable to a 1⁺ valencystate.

The ligands L and X may be bridged to each other and if two ligands Land/or X are present, they may be bridged. The metallocenes may befull-sandwich compounds having two ligands L which are cyclopentadienylgroups or half-sandwich compounds having one ligand L only which is acylcopentadienyl group.

For the purposes of this patent specification the term "metallocene" isdefined to contain one or more cyclopentadienyl moiety in combinationwith a transition metal of the Periodic Table of Elements. In oneembodiment the metallocene catalyst component is represented by thegeneral formula (Cp)_(m) MR_(n) R'_(p) wherein Cp is a substituted orunsubstituted cyclopentadienyl ring; M is a Group IV, V or VI transitionmetal; R and R' are independently selected halogen, hydrocarbyl group,or hydrocarboxyl groups having 1-20 carbon atoms; m=1-3, n=0-3, p=0-3,and the sum of m+n+p equals the oxidation state of M. In anotherembodiment the metallocene catalyst is represented by the formulas:

    (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p-x

    R".sub.s (.sub.5 R'.sub.m).sub.2 MeQ'

wherein Me is a Group IV, V, or VI transition metal, C₅ R'_(m) is asubstituted cyclopentadienyl each R', which can be the same or differentas hydrogen, alkenyl, aryl alkaryl or arylalkyl radical having from 1 to20 carbon atoms or two carbon atoms joined together to form a part of aC₄ to C₆ ring, R" is one or more of or a combination of carbon,germanium, silicon, phosphorous or nitrogen atom containing radicalsubstituting on and bridging two C₅ R"_(m) rings or bridging one C₅R'_(m) ring back to Me, when p=0 and x=1 otherwise x is always equal to0, each Q which can be the same or different as an aryl alkyl, alkenyl,alkaryl, or arylalkyl radical having from 1 to 20 carbon atoms orhalogen, Q' is an alkylidene radical having from 1 to 20 carbon atoms, sis 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, mis 4 and p is 1.

Various forms of the catalyst system of the metallocene type may be usedin the polymerization process of this invention. Exemplary of thedevelopment of metallocene catalysts in the art for polymerization ofethylene is the disclosure of U.S. Pat. No. 4,871,705 (Hoel), U.S. Pat.No. 4,937,299 (Ewen et al.), EP-A 0129368, published on Jul. 26, 1989,and U.S. Pat. No. 5,017,714 and U.S. Pat. No. 5,120,867 to Welborn, Jr.These publications teach the structure of the metallocene catalysts andinclude alumoxane as the co-catalyst. There are a variety of methods forpreparing alumoxane, one of which is described in U.S. Pat. No.4,665,208.

For purposes of this patent specification, the terms "co-catalysts" or"activators" are used interchangeably and are defined to be any compoundor component which can activate a bulky ligand transition metalcompound. In one embodiment the activators generally contain a metal ofGroup II and III of the Periodic Table of Elements. In the preferredembodiment, the bulky transition metal compounds are metallocenes, whichare activated by trialkylaluminum compounds, alumoxanes both linear andcyclic, or ionizing ionic activators or compounds such as tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, which ionize the neutralmetallocene compound. Such ionizing compounds may contain an activeproton, or some other cation associated with but not coordinated, oronly loosely coordinated to the remaining ion of the ionizing ioniccompound. Such compounds are described in EP-A 0520732, EP-A 0277003 andEP-A 0277004, published on Aug. 3, 1988, and U.S. Pat. No. 5,153,157,U.S. Pat. No. 5,198,401 and U.S. Pat. No. 5,241,025. Further, themetallocene catalyst component can be a monocyclopentadienyl heteroatomcontaining compound. This heteroatom is activated by either an alumoxaneor an ionic activator to form an active polymerization catalyst systemto produce polymers useful in this invention. These types of catalystsystems are described in, for example, WO-A 92/00333 published Jan. 9,1992, U.S. Pat. No. 505,747S, U.S. Pat. No. 5,096,867, U.S. Pat. No.5,055,438 and U.S. Pat. No. 5,227,440, and EP-A 20 91/04257. Inaddition, the metallocene catalyst useful in this invention can includenon-cyclopentadienyl catalyst components, or ancillary ligands such asboroles or carbollides in combination with a transition metal.Additionally, it is not beyond the scope of this invention that thecatalysts and catalyst systems may be those described in U.S. Pat. No.5,064,802 and WO-A 93/08221 and WO-A 93/08199 published Apr. 29, 1993.All the catalyst systems of the invention may be, optionally,prepolymerized or used in conjunction with an additive or scavengingcomponent to enhance catalytic productivity.

Preferred metallocene catalysts according to the present inventioninclude: racemic 1, 1'dimethylsilanylene-bis (3-methylcyclopentadienyl)!zirconium dichloride; 1,1'-dimethylsilanylene-bis (indenyl)!zirconiumdichloride; 1, 1'-dimethylsilanylene-bis(4,5,6,7-tetrahydroindenyl)! zirconium dichloride;1,1'-(1,1,2,2-tetramethyldisilanylene)-bis (3-methylcyclopentadienyl)!zirconium dichloride; 1,1'-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)) zirconium dichloride;1,1'-dimethylsilanylene-bis (3-trimethylsilanylcyclopentadien)!zirconium dichloride; 1,1'-(1,1,2,2-tetramethyldisilanylene)-bis(3-trimethylsilanylcyclopentadienyl)! zirconium dichloride;1,1'-(1,1,3,3-tetramethyldisiloxanylene)-bis(4,5,6,7-tetrahydroindenyl)! zirconium dichloride;1,1'-(1,1,4,4-tetramethyl-1,4-disilanylbutylene)-bis(4,5,6,7-tetrahydroindenyl)! zirconium dichloride;(1,1'-(2,2-dimethyl-2-silapropylene)-bis(3-methylcyclopentadienyl)!zirconium dichloride.

POLYMERS

The polymers can be prepared by polymerizing monomer mixtures comprisingethylene and α-olefins, preferably from 3 to 4 carbon atoms, but up to16 carbon atoms, in the presence of a metallocene catalyst systemcomprising at least one metallocene (e.g., a cyclopentadienyl-transitionmetal compound) and an activator, e.g., alumoxane compound. Thecomonomer content can be controlled through selection of the metallocenecatalyst component and by controlling partial pressure or concentrationof the monomers.

As such, the polymers which are useful in the present invention arepolymers containing at least one carbon-carbon double bond (olefinic orethylenic) unsaturation. Thus, the maximum number of functional groupsper polymer chain is limited by the number of double bonds per chain.

Useful polymers in the present invention include polyalkenes includinghomopolymers, copolymers (used interchangeably with interpolymer) andmixtures. Homopolymers and interpolymers include those derived frompolymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2to about 6 carbon atoms.

Particular reference is made to the α-olefin polymers made usingorganometallic coordination compounds. A particularly preferred class ofpolymers are ethylene-α-olefin copolymers such as those disclosed inU.S. Pat. No. 5,017,299. The polymer unsaturation can be terminal,internal or both. Preferred polymers have terminal unsaturation,preferably a high degree of terminal unsaturation. Terminal unsaturationis the unsaturation provided by the last monomer unit located in thepolymer. The unsaturation can be located anywhere in this terminalmonomer unit. Terminal olefinic groups include vinylidene (i.e.,ethenylidene) unsaturation, R^(a) R^(b) C=CH₂ ; trisubstituted olefinunsaturation, R^(a) R^(b) C=CR^(c) H; vinyl unsaturation, R^(a) HC =CH₂; 1,2-disubstituted terminal unsaturation, R^(a) HC=CHR^(b) ; andtetra-substituted terminal unsaturation, R^(a) R^(b) C=CR^(c) R. Atleast one of R^(a) and R^(b) is a polymeric group of the presentinvention, and the remaining R^(b), R^(c) and R^(d) are hydrocarbongroups such as hydrogen, hydrocarbyl, aryl, substituted aryl orsubstituted hydrocarbyl.

The polymer employed in this invention comprises polymer chains, atleast about 30 percent of which possess terminal vinylideneunsaturation. Preferably at least about 50 percent, more preferably atleast about 60 percent, and most preferably at least about 75 percent(e.g., 75-98%), of such polymer chains exhibit terminal vinylideneunsaturation. The percentage of polymer chains exhibiting terminalvinylidene unsaturation may be determined by FTIR spectroscopicanalysis, titration, or C¹³ NMR.

The olefin monomers are preferably polymerizable terminal olefins; thatis, olefins characterized by the presence in their structure of thegroup -R--C =CH₂, where R is hydrogen or a hydrocarbon group. However,polymerizable internal olefin monomers (sometimes referred to in theliterature as medial olefins) characterized by the presence within theirstructure of the group: ##STR4##

can also be used to form the polyalkenes. When internal olefin monomersare employed, they normally will be employed with terminal olefins toproduce polyalkenes which are interpolymers. For this invention, aparticular polymerized olefin, will be deemed a terminal olefin. Thus,pentadiene-1,3 (i.e., piperylene) is deemed to be a terminal olefin.

While the polyalkenes generally are hydrocarbon polyalkenes, they cancontain substituted hydrocarbon groups such as lower alkoxy, lower alkylmercapto, hydroxyl, mercapto, and carbonyl, provided the non-hydrocarbonmoieties do not substantially interfere with the functionalization orderivatization reaction of this invention. When present, suchsubstituted hydrocarbon groups normally will not contribute more thanabout 10% by weight of the total weight of the polyalkenes. Since thepolyalkene can contain such non-hydrocarbon substituent, it is apparentthat the olefin monomers from which the polyalkenes are made can alsocontain such substituents. As used herein, the term "lower" when usedwith a chemical group such as in "lower alkyl" or 37 lower alkoxy" isintended to describe groups having up to seven carbon atoms.

The polyalkenes may include aromatic groups and cycloaliphatic groupssuch as would be obtained from polymerizable cyclic olefins orcycloaliphatic substituted-polymerizable acrylic olefins. There is ageneral preference for polyalkenes derived from homopolymers andcopolymers of terminal hydrocarbon olefins of 2 to 16 carbon atoms. Thisfurther preference is qualified by the proviso that, while interpolymersof terminal olefins are usually preferred, interpolymers optionallycontaining up to about 40% of polymer units derived from internalolefins of up to about 16 carbon atoms are also within a preferredgroup. A more preferred class of polyalkenes are those selected from thegroup consisting of homopolymers and interpolymers of terminal olefinsof 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. However,another preferred class of polyalkenes are the latter, more preferredpolyalkenes optionally containing up to about 25% of polymer unitsderived from internal olefins of up to about 6 carbon atoms.

Specific examples of terminal monomers which can be used to prepare thepolyalkenes include ethylene, propylene, butene-1, pentene-1,butadiene-1,3, and 5 pentadiene-1,3.

Useful polymers include α-olefin homopolymers and interpolymers, andethylene-α-olefin copolymers and terpolymers. Specific examples ofpolyalkenes include polypropylenes, poly-1-butenes, ethylene-propylenecopolymers, ethylene-1-butene copolymers, and propylene-1-butenecopolymers.

Preferred polymers are polymers of ethylene and at least one α-olefinhaving the formula H₂ C=CHR⁴ wherein R⁴ is a straight chain or branchedchain alkyl radical comprising 0 to 14 carbon atoms and wherein thepolymer contains a high degree of terminal vinylidene unsaturation.Preferably, R⁴ in the above formula is alkyl of from 1 to 8 carbon atomsand more preferably is alkyl of from 1 to 2 carbon atoms. Therefore,useful comonomers with ethylene in this invention include propylene,1-butene, hexene-1, octene-1, etc., and mixtures thereof (e.g., mixturesof propylene and 1-butene, and the like). Preferred polymers arecopolymers of ethylene and propylene and ethylene and butene-1.

The molar ethylene content of the polymers employed is preferably in therange of between about 20 to about 80%, and more preferably betweenabout 30 to about 70%. When butene-1 is employed as a comonomer withethylene, the ethylene content of such a copolymer is most preferablybetween about 20 to about 45 weight %, although higher or lower ethylenecontents may be present. The most preferred ethylene-butene-1 copolymersare disclosed in co-pending U.S. patent application, Ser. No. 992,192,filed Dec. 17, 1992. The preferred method for making low molecularweight ethylene-α-olefin copolymers is described in U.S. patentapplication, Ser. No. 992,690, filed Dec. 17, 1992.

Preferred ranges of number average molecular weights of polymers for useas precursors for dispersants are from 300 to 10,000, preferably from700 to 5,000, most preferably from 1,500 to 3,000. A convenient methodfor such determination is by size exclusive chromatography (also knownas gel permeation chromatograph (GPC)) which additionally providesmolecular weight distribution information. Such polymers generallypossess an intrinsic viscosity (as measured in tetralin at 135° C.) ofbetween 0.025 and 0.6 dl/g, preferably between 0.05 and 0.5 dl/g, mostpreferably between 0.075 and 0.4 dl/g. These polymers preferably exhibita degree of crystallinity such that, when grafted, they are essentiallyamorphous.

The preferred ethylene-a-olefin polymers are further characterized inthat up to about 95% and more of the polymer chains possess terminalvinylidene-type unsaturation. Thus, one end of such polymers will be ofthe formula POLY-C(R¹¹)=CH₂ wherein R¹¹ is C₁ to C₁₈ alkyl, preferablyC₁ to C₈ alkyl, and more preferably methyl or ethyl and wherein POLYrepresents the polymer chain. A minor amount of the polymer chain cancontain terminal ethenyl unsaturation, i.e., POLY-CH=CH₂, and a portionof the polymers can contain internal mono-unsaturation, e.g.,POLY-CH=CH(R¹¹), wherein R¹¹ is as defined above.

AMINES

Suitable amines for use in forming fuel additives or detergents aredisclosed in U.S. Pat. No. 3,438,757 (Honnen et al.), which issued onApr. 15, 1969, and include N-substituted amines and alkylene polyamines.

Illustrative compositions of desired N-substituted amines include, butare not limited to, polypropenyl amine, polyisobutenyl amine,N-polyisobutenyl dimethylamine, N-polyisobutenyl methylethylamine,N-polypropenyl diethylamine, N-polypropenyl di(2-hydroxyethyl) amine,N-polyisobutenyl N-methyl aniline, N-polyisobutenyl morpholine,N-polyisobutenyl piperidiene, N-poly(1-butene) propylamine,N-polypropenyl N-(2-hydroxyethyl) amine, etc.

Preferred alkylene polyamines which are substituted with the hydrocarbonradical may be derived from such alkylene amines as ethylene diamine,diethylene triamine, tetraethylene pentamine, nonaethylene decamine,1,2-propylene diamine, tetramethylene diamine, etc.

In many instances a single compound will not be used as a reactant inthe preparation of the dispersants of the present invention. That is,mixtures will be used in which one or two compounds will predominate andthe average composition or molecular weight is indicated. Illustrativecompounds within the above formula are as follows: N-polyisobutenylethylene diamine, N-polypropenyl ethylene diamine,N-poly(l-butenyl)ethylene diamine, N- (alternating copolymers ofethylene and isobutylene may be achieved by the cationic polymerizationof 4-methylpentene-1), N-poly(1-pentenyl) diethylene triamine,N-polypropenyl trimethylene diamine, N-polyisobutenyl trimethylenediamine, N-polypropenyl di- (trimethylene) triamine, N-polyisobutenyldi(trimethylene)triamine, N-polyisobutenyl 1,2-propylene diamine,N-polyisobutenyl di(1,2-propylene) triamine, N-polypropenyl triethylenetetramine, N--polyisobutenyl triethylene tetramine, N-(alternatingcopolymer of ethylene and isobutylene) triethylene tetramine,N-polypropenyl tetraethylene pentamine, N-polyisobutenyl tetraethylenepentamine, N-polyisobutenyl pentaethylene hexamine, etc.

The following polyhydrocarbon radical substituted alkylene polyaminecompositions are also desirable: N,N'di(polypropenyl)diethylenetriamine, N,N'-di(polyisobutenyl) diethylene triamine,N,N'-di(polyisobutenyl) triethylene tetramine, N,N'-di(polypropenyl)tetraethylene pentamine, N'N'-di(polyisobutenyl) tetraethylenepentamine, N,N',N'-tri(polyisobutenyl) tetraethylene pentamine,N,N'-di(polyisobutenyl) 2-aminoethylpiperazine,N,N'-di(poly-l-butenyl)triethylene tetramine, N,N'-di(polyisobutenyl)di(trimethylene) triamine, etc.

The preferred compositions for use in making fuel detergents are thosehaving the straight chain alkylene polyamines, particularly ethylenediamine and polyethylene polyamines.

Amines which are useful in forming dispersants for use in lubricatingapplications are set forth in U.S. Pat. No. 4,234,435 (Meinhardt), whichissued on Nov. 18, 1980. The amine for use in forming lubricatingdispersants, characterized by the presence within its structure of atleast one H--N< group, can be a monoamine or polyamine compound.Preferably, the amine contains at least one primary amino groups (i.e.,-NH₂) and more preferably the amine is a polyamine, especially apolyamine containing at least two H--N<groups, either or both of whichare primary or secondary amines.

The amines can be aliphatic, cycloaliphatic, aromatic, or heterocyclic,including aliphatic-substituted cycloaliphatic, aliphatic-substitutedaromatic, aliphatic-substituted heterocyclic, cycloaliphatic-substitutedaliphatic, cycloaliphatic-substituted aromatic,cycloaliphatic-substituted heterocyclic, aromatic-substituted aliphatic,aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic,heterocyclic-substituted aliphatic, heterocyclic-substituted alicyclic,and heterocyclic-substituted aromatic amines and may be saturated orunsaturated. If unsaturated, the amine will be free from acetylenicunsaturation (i.e., -C=C-). The amines may also contain non-hydrocarbonsubstituents or groups.

With the exception of the branched polyalkylene polyamine, thepolyoxyalkylene polyamines, and the high molecular weighthydrocarbyl-substituted amines, the amines ordinarily contain less thanabout 40 carbon atoms in total and usually not more than about 20 carbonatoms in total.

The additives, particularly those adapted for use as dispersants orviscosity modifiers, can be incorporated into a lubricating oil in anyconvenient way. Thus, they can be added directly to the oil bydispersing or dissolving the same in the oil. Such blending into theadditional lube oil can occur at room temperature or elevatedtemperatures. Alternatively the additives may be first formed intoconcentrates, which are in turn blended into the oil. Such dispersantconcentrates will typically contain as active ingredients from 10 to 80wt. %, typically 20 to 60 wt. %, and preferably from 40 to 50 wt. %,additive, (based on the concentrate weight) in base oil.

The additives may be mixed with other additives selected to perform atleast one desired function. Typical of such additional additives aredetergents, viscosity modifiers, wear inhibitors, oxidation inhibitors,corrosion inhibitors, friction modifiers, foam inhibitors, rustinhibitors, demulsifiers, antioxidants, lube oil flow improvers, andseal swell control agents.

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates or packages comprisingconcentrated solutions or dispersions of the subject additives of thisinvention together with one or more of the other additives. Dissolutionof the additive concentrate into lubricating oil may be facilitated bysolvents and by mixing accompanied with mild heating, but this in notessential. The final formulations may employ typically 2 to 20 wt. %,e.g., about 10 wt. %, of the additive package with the remainder beingbase oil.

EXAMPLE 1 (Comparative)

This example compares the conversion of various polymeric olefins topolymeric aldehydes under hydroformylating conditions. The polymers were(1) a boron-fluoride catalyzed cationic polyisobutylene, (2) anethylene-propylene copolymer according to the present invention, (3) apoly-N-butylene, and (4) an aluminum chloride catalyzed polyisobutylene.Each polymer was separately charged, at room temperature, into arocking, two liter volume, stainless steel autoclave fitted withinternal cooling coils, together with a dicobalt octacarbonyl catalyst.The autoclave was then sealed and pressurized with 1,000 psig (6.996×10⁶N/m²) of carbon monoxide and hydrogen (volume ratio of 1/1). Theautoclave was then heated to 120° C. for 5 hours with rocking to theindicated reaction time, cooled to room temperature and then thecontents were removed. The product was demetaled of cobalt by shakingover a 30 minute period with 300 ml of 10 wt.% aqueous acetic acid at 30to 45° C. in an atmosphere of air at one atmosphere pressure. Thedemetaling procedure was repeated twice with fresh aqueous acetic acid.The product was then washed three times with water and the solventremoved under vacuum by heating at 40 to 70° C. Conversion wasdetermined by the standard AI test. The results are set forth below inTable 1.

                  TABLE 1                                                         ______________________________________                                                     Polymer Heptane                                                                              Catalyst*                                                                            Percent of Conversion                      Sample                                                                              Mn     (grams) (grams)                                                                              (grams)                                                                              to Polymeric Aldehyde                      ______________________________________                                        1     1000   284.7   751.7  4.5    30.9                                       2     1000   307.3   665.5  5.5    70.8                                       3      500   388.3   657.6  5.6    18.4                                       4     1000   380.0   688.9  6.0    37.6                                       ______________________________________                                         *Denotes a dicobalt octacarbonyl catalyst.                               

Table 1 compares the conversion to hydroformylated products of threetypes of polybutenes to that of the metallocene catalyzedethylene-propylene copolymer of the present invention. The lower heatingtemperature of 120° C. tends to favor aldehyde rather than alcohol 35formation. The yield of functionalized ethylene-propylene copolymer wasalmost twice that observed with any of the functionalized polybutenepolymers.

EXAMPLE 2 (Comparative)

This example compares the conversion of various polymeric olefins topolymeric alcohols under hydroformylating conditions. The polymers were(1) a boron-fluoride catalyzed cationic polyisobutylene, (2) aethylene-propylene copolymer according to the present invention, (3) apoly-N-butylene, and (4) an aluminum chloride catalyzed polyisobutylene.Each polymer was separately charged, at room temperature, into arocking, two liter volume, stainless steel autoclave fitted withinternal cooling coils, together with a dicobalt octacarbonyl catalyst.The autoclave was then sealed and pressurized with 1,000 psig (6.996×106N/m²) of carbon monoxide and hydrogen (volume ratio of 1/1). Theautoclave was then heated to 170° C. for 5 hours with rocking to theindicated reaction time, cooled to room temperature and then thecontents were removed. The product was demetaled of cobalt by shakingover a 30 minute period with 300 ml of 10 wt. % aqueous acetic acid at30 to 45° C. in an atmosphere of air at one atmosphere pressure. Thedemetaling procedure was repeated twice with fresh aqueous acetic acid.The product was then washed three times with water and the solventremoved under vacuum by heating at 40 to 70° C.

Next, the polymeric aldehydes in the demetaled, reaction product werereduced to alcohols by treatment with sodium borohydride. This was byaddition of 10 to 15 grams of sodium borohydride powder and 50 to 100 mlof isopropanol, with stirring, for two to three hours (with cooling froman ice bath to maintain the exothermic reaction at 45 to 50° C.). Theproduct was then filtered, using filter aid on paper, washed with water,5% aqueous hydrochloric acid, and then twice more with water. Next, thesolvent and isopropanol residue were removed under vacuum by heating at40 to 70° C. Conversion was determined by the standard AI test. Theresults are set forth below in Table 2.

                  TABLE 2                                                         ______________________________________                                                      Polymer Heptane                                                                             Catalyst*                                                                            Percent of Conversion                      Sample Mn     (grams) ()    (grams)                                                                              to Polymeric Aldehyde                      ______________________________________                                        1      1000   383.9   725.8 6.2    68.4                                       2      1100   391.4   703.6 6.5    82.9                                       3       500   389.7   664.7 6.1    47.7                                       4      1000   495.0   525.0 7.0    71.9                                       ______________________________________                                         *Denotes a dicobalt octacarbonyl catalyst.                               

Table 2 compares the conversion to hydroformylated products of threetypes of polybutenes to that of the metallocene catalyzedethylene-propylene copolymer of the present invention. The higherheating temperature of 170° C. tends to favor alcohol rather thanaldehyde formation. The reaction products were further reduced withsodium borohydride to convert any remaining aldehyde to alcohol. Theyield of functionalized ethylene-propylene copolymer was substantiallyhigher than that observed with any of the functionalized polybutenepolymers.

EXAMPLE 3

30 grams of an ethylene-propylene copolymer formed in accordance withthe present invention containing about 85% vinylidene olefin structureand having a number average molecular weight (Mn) of 1600 was combinedwith 30 grams of hexane, 3.8 grams of 3-dimethylamino propylamine and 26mg of rhodium dicarbonyl acetylacetonate (Rh(CO)₂ AcAc). The reactionmixture was pressured to 1,000 psi (6.895×10⁶ N/m²) with carbon monoxideand hydrogen in a 1/1 ratio and heated at 150° C. for 28 hours.

Solvent and excess amine were removed by heating and vacuum. The polymerproduct contained 86% aminated polymer (active ingredient) determined bycolumn chromatography. Elemental nitrogen by duplicate analysis was1.37% (1.63% theory for 100% conversion).

EXAMPLE 4

Example 3 was repeated using a cationic polymer of poly-n-butene (PNB).This polymer has a high trisubstituted olefin content and a numberaverage molecular weight (Mn) of 559. After 28 hours reaction time, theproduct contained only 39% aminated polymer.

EXAMPLE 5

Example 3 above was repeated using a 42 hour reaction time. Theconversion (AI) was 90.0% and elemental nitrogen was 1.36%.

EXAMPLE 6

The method of Example 3 above was repeated using an ethylene-butenepolymer with a number average weight of 2,000. The product had anaminated polymer content 30 of 83.2% and an elemental nitrogen contentof 1.03%.

EXAMPLE 7

The method of Example 3 above was repeated using 6.5 mg of catalyst anda 120°C. reaction temperature. The product had an aminated polymercontent of 88.1% and an elemental nitrogen content of 1.41%.

EXAMPLE 8

The method of Example 3 above was repeated using a butylene-propylenepolymer with a number average weight of 2,140. The product had anaminated polymer content of 69.3% and an elemental nitrogen content of0.64%.

EXAMPLE 9

The method of Example 3 above was repeated using aminoethylpiperazine asthe amine (2 mole of amine per mole of ethylene-butene polymer) and 52mg of catalyst. The product had an aminated polymer content of 88.8% andan elemental nitrogen content of 2.07% (theory 2.43%).

EXAMPLE 10

The method of Example 3 above was repeated using 105 mg oftriphenylphosphine ligand and 52 mg of catalyst. The product had anaminated polymer content of 77.9% and an elemental nitrogen content of1.18%.

EXAMPLE 11

The method of Example 3 above was repeated using a 1-butene polymerprepared via a metallocene catalyst with a number average weight of 978.The product had an aminated polymer content of 66.5% and an elementalnitrogen content of 1.60%.

While we have shown and described several embodiments in accordance withour invention, it is to be clearly understood that the same aresusceptible to numerous changes apparent to one skilled in the art.Therefore, we do not wish to be limited to the details shown anddescribed but intend to show all changes and modifications which comewithin the scope of the appended claims.

What is claimed is:
 1. A saturated polymer having a terminal aldehyde orhydroxyl substituent, a M_(n) of about 300 to 10,000, and derived from apolyolefin derived from a monomer of the formula H₂ C=CHR⁴ wherein R⁴ ishydrogen or a straight or branched chain alkyl radical, said polyolefinhaving at least about 30 % terminal vinylidene unsaturation.
 2. Thesaturated polymer according to claim 1 wherein said polyolefin ispolymerized from alkene and α-olefin monomers with a metallocenecatalyst.
 3. The saturated polymer according to claim 2 wherein saidpolyolefin is an ethylene/α-olefin, a propylene/butene-1 copolymer, or abutene-1 polyolefin.
 4. A polymeric hydroformylation reaction productwhich is formed by reacting:a polyolefin having terminal unsaturationand an M_(n) of about 300 to about 10.000, said polyolefin being derivedfrom a monomer of the formula H₂ C=CHR⁴, wherein R⁴ is hydrogen or astraight or branched chain alkyl radical: hydrogen: and carbon monoxidein the presence of a hydroformylation catalyst, under conditionseffective to hydroformylate said polyolefin and wherein said polymerichydroformylation product is further reductively aminated to form anitrogen-containing polymeric product having an alkylamino substituentor wherein said polymeric hydroformylation product is further reducedcyanoalkylated and hydrogenated to form an aminated polymer.
 5. Apolymeric aminomethylation reaction product having an alkylaminosubstituent and wherein said reaction product is formed by reacting:apolyolefin having terminal unsaturation, wherein said terminalunsaturation comprises at least 30% terminal vinylidene unsaturation,and a M_(n) of about 300 to 10.000, said polyolefin being derived from amonomer of the formula H₂ C=CHR⁴, wherein R⁴ is hydrogen or a straightor branched chain alkyl radical: hydrogen: and carbon monoxide in thepresence of an amine and a hydroformylation catalyst. under conditionseffective to aminomethylate said polyolefin.